CN105244491A - Technology for preparing lithium titanate lithium-ion battery anode material - Google Patents

Technology for preparing lithium titanate lithium-ion battery anode material Download PDF

Info

Publication number
CN105244491A
CN105244491A CN201510678156.XA CN201510678156A CN105244491A CN 105244491 A CN105244491 A CN 105244491A CN 201510678156 A CN201510678156 A CN 201510678156A CN 105244491 A CN105244491 A CN 105244491A
Authority
CN
China
Prior art keywords
lithium titanate
ion battery
technique
lithium
manufacture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510678156.XA
Other languages
Chinese (zh)
Inventor
黄小丽
岳波
向中林
王俊安
周俊杰
张航
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN KENENG LITHIUM BATTERY Co Ltd
Original Assignee
SICHUAN KENENG LITHIUM BATTERY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SICHUAN KENENG LITHIUM BATTERY Co Ltd filed Critical SICHUAN KENENG LITHIUM BATTERY Co Ltd
Priority to CN201510678156.XA priority Critical patent/CN105244491A/en
Publication of CN105244491A publication Critical patent/CN105244491A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a technology for preparing a lithium titanate lithium-ion battery anode material. The technology comprises the following steps: (1) with anatase nano TiO2 as a raw material, preparing nanoscale precursor powder of a Li-Ti-O ternary system under hydrothermal reaction conditions at atmospheric pressure; (2) preparing suspension slurry from the raw material, auxiliary materials and an additive, forming liquid drops from the solution through a special nozzle at certain pressure, spaying the liquid drops into roasting equipment with a constant temperature within an appointed range in a mist form, and carrying out a drying treatment, so as to obtain spherical lithium titanate precursor powder. The technical effects are achieved that the technological design is reasonable; the risk is relatively low; the improvement effect on the conductivity is relatively good; the tap density of the powder is ensured; and the specific volumetric capacity of the electrode material is improved.

Description

A kind of technique manufacturing lithium titanate lithium ion battery negative material
Technical field
The present invention relates to lithium ion battery negative material and manufacture field, particularly, relate to a kind of technique manufacturing lithium titanate lithium ion battery negative material.
Background technology
Lithium ion battery: be a kind of secondary cell (rechargeable battery), it mainly rely on lithium ion between a positive electrode and a negative electrode movement carry out work.In charge and discharge process, Li+ comes and goes between two electrodes and embeds and deintercalation: during charging, and Li+ is from positive pole deintercalation, and embed negative pole through electrolyte, negative pole is in rich lithium state; Then contrary during electric discharge.Battery generally adopts material containing elemental lithium as electrode, is the representative of modern high performance battery.
Lithium system battery is divided into lithium battery and lithium ion battery.What mobile phone and notebook computer used is all lithium ion battery, and usual people's custom is called lithium battery, and real lithium battery is large due to danger, is seldom applied to day electronic product.
Lithium titanate (Li 4ti 5o 12) make the fast charging and discharging performance of lithium ion battery than conventional lithium ion battery of negative material, cycle performance is better, security performance is higher.Li 4ti 5o 12as negative material and LiFePO 4, LiCo0 2, LiMn0 4, LiNi0 2lithium ion battery, all-solid-state battery, hybrid super capacitor can be formed with active carbon etc., show good circulation and security performance.Therefore, with Li 4ti 5o 12the lithium ion battery making negative material is expected to for current mainstream electronic product.
Traditional Hydrothermal Synthesis normally carries out under elevated temperature and pressure conditions, and its product purity is high, good dispersion, granularity are easy to control, but the condition of high temperature, high pressure adds industrial difficulty and production cost, also has certain industrial hazard simultaneously.
Because the electric conductivity of the lithium titanate material both at home and abroad manufactured now is not ideal enough, part research at present adds conductive component such as carbon black, acetylene black, metal powder etc. and improves the conductivity of electrode body producing in lithium titanate powder.But the method added after this adopts binder both to be combined, be difficult to make the interface of conductive component and lithium titanate powder have good close contact, the improvement effect of electric conductivity is affected, also reduce further the tap density of powder simultaneously, the volume and capacity ratio of electrode material is decreased.
In sum, present inventor, in the process realizing invention technical scheme in the embodiment of the present application, finds that above-mentioned technology at least exists following technical problem:
In the prior art, the dangerous property of technique of existing manufacture lithium titanate lithium ion battery negative material is higher, and it is poor that electric conductivity improves effect, reduces the tap density of powder, makes the technical problem that the volume and capacity ratio of electrode material decreases.
Summary of the invention
The invention provides a kind of technique manufacturing lithium titanate lithium ion battery negative material, the dangerous property of technique solving existing manufacture lithium titanate lithium ion battery negative material is higher, it is poor that electric conductivity improves effect, reduce the tap density of powder, make the technical problem that the volume and capacity ratio of electrode material decreases, achieve technological design reasonable, danger is lower, it is better that electric conductivity improves effect, ensure the tap density of powder, make the technique effect that the volume and capacity ratio of electrode material raises.
For solving the problems of the technologies described above, the embodiment of the present application provides a kind of technique manufacturing lithium titanate lithium ion battery negative material, and described technique comprises:
Step 1: with anatase type nano TiO 2for raw material, under hydrothermal reaction condition, manufacture the nanoscale precursor powder of Li-Ti-O ternary system at ambient pressure;
Step 2: raw material, auxiliary material, interpolation auxiliary agent are made suspension slurry, then solution is passed through special nozzle under a certain pressure, formation drop nebulizes and sprays into temperature constant in the roasting apparatus of specified scope, carries out drying process, obtains spherical lithium titanate precursor powder.
Further, organic media is added in described step 2 as bonding agent and carbon source.
Further, 10 minutes are less than or equal to described withering drying time.
Further, the steady temperature of described roasting apparatus is 1000 degree.
Further, described technique also comprises and carries out conductive carbon coating modification.
The one or more technical schemes provided in the embodiment of the present application, at least have following technique effect or advantage:
Achieve technological design reasonable, danger is lower, and it is better that electric conductivity improves effect, ensured the tap density of powder, made the technique effect that the volume and capacity ratio of electrode material raises.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the technique manufacturing lithium titanate lithium ion battery negative material in the embodiment of the present application.
Embodiment
The invention provides a kind of technique manufacturing lithium titanate lithium ion battery negative material, the dangerous property of technique solving existing manufacture lithium titanate lithium ion battery negative material is higher, it is poor that electric conductivity improves effect, reduce the tap density of powder, make the technical problem that the volume and capacity ratio of electrode material decreases, achieve technological design reasonable, danger is lower, it is better that electric conductivity improves effect, ensure the tap density of powder, make the technique effect that the volume and capacity ratio of electrode material raises.
In order to better understand technique scheme, below in conjunction with Figure of description and concrete execution mode, technique scheme is described in detail.
Below in conjunction with embodiment and accompanying drawing, to the detailed description further of the present invention's do, but embodiments of the present invention are not limited thereto.
Embodiment 1:
The application adopts a kind of new technology of synthesizing high quality nano level lithium titanate lithium ion battery negative material at constant pressure hydro-thermal synthesis presoma and subsequent spray drying-granulating, high temperature solid-state roasting.Clear reference diagram 1, the application has completed laboratory lab scale research work, and research obtains with anatase type nano TiO 2for raw material, under normal pressure, hydro-thermal reaction manufactures the condition of nanoscale precursor; Have selected suitable organic media as bonding agent and carbon source; Have studied the specific capacity of compound high-valence cationic doping vario-property on lithium titanate powder and the impact of tap density; Obtain the technical datas such as suitable synthesis temperature, generated time.
On the basis of previous experiments room lithium ionic cell cathode material lithium titanate achievement in research, the existing research and development ability of company and condition, for feasibility and the adaptability of checking technique, technology when output is amplified, the application intends the scale up test research carrying out the nano lithium titanate of 100T/a, and main research comprises the sizing of existing equipment improvement, corollary equipment; The optimization of the technological parameters such as proportion scale, hydrothermal synthesizing condition, atomization drying condition, roasting condition.Form complete technology code, equipment regulation and technical standard of enterprise by scale up test drying and realize the steady production of minimum 50 batches.
The application intends adopting advanced dry nebulization technique to produce the lithium titanate powder of little crystal grain, high-tap density.The process of dry nebulization can be described as briefly: first raw material in need for institute, auxiliary material, interpolation auxiliary agent etc. are made suspension slurry, then solution is passed through special nozzle under a certain pressure, the very tiny drop of formation nebulizes and sprays into temperature constant in the roasting apparatus of specified scope, complete drying in a short period of time, granularity can be obtained and be less than the spherical lithium titanate precursor powder that 2 μm even reach sub-micron.
The application intends adding some organic components filtered out especially in advance when precursor pulp is prepared, and is to make slurry have suitable mobility and viscosity, preventing paste deposition on the one hand, simultaneously the particle properties of optimizing drying product.Meanwhile, suitable binding agent contributes to the molding, granulating of powder granule, can improve spheroid intensity.On the other hand, for improving the conductance of material, it is necessary for carrying out conductive carbon coating modification to manufacture high quality nano lithium titanate, therefore, organic media again can as the carbon source of product, the carbon element that it is matrix that formation has with carbon six ring structure containing large π key, thus form at lithium titanate grain surface the thin layer that one deck combines closely, conductivity is good, significantly reduce the addition of conductive component, both improved the electric conductivity of powder, do not reduce again overall tap density and specific capacity.On the other hand, the employing of carbon cladding process can stop crystal grain growing up in high temperature solid state reaction process, makes primary particle keep the nanoscale of Hydrothermal Synthesis precursor.
Therefore, the lithium titanate product adopting this technique to synthesize, both ensure that spherical morphology, and the size of guaranteed primary particle remains on nanoscale, improves the combination properties such as the conductivity of material, specific capacity, tap density.
Lithium titanate is spinel structure, has stable state.Under the effect of electric field, lithium ion can in lattice directional migration, show certain conductivity, the direct shadow of lithium migration rate its ring the level of conductance and actual capacity of material.Carrying out metal-doped main purpose to lithium titanate has two: one to be electrode potential in order to reduce it, improves battery energy density; One is the conductivity improving material, reduces resistance and polarization.The application intends adopting Mg 2+, Zn 2+, Al 3+, Cr 3+soluble-salt Deng high volence metal ion carries out doping treatment under liquid-phase condition, ensures Doped ions uniformity in the product.On this basis, carry out many kinds of metal ions codope and carry out study on the modification.
Technical scheme in above-mentioned the embodiment of the present application, at least has following technique effect or advantage:
Achieve technological design reasonable, danger is lower, and it is better that electric conductivity improves effect, ensured the tap density of powder, made the technique effect that the volume and capacity ratio of electrode material raises.
Although describe the preferred embodiments of the present invention, those skilled in the art once obtain the basic creative concept of cicada, then can make other change and amendment to these embodiments.So claims are intended to be interpreted as comprising preferred embodiment and falling into all changes and the amendment of the scope of the invention.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.

Claims (5)

1. manufacture a technique for lithium titanate lithium ion battery negative material, it is characterized in that, described technique comprises:
Step 1: with anatase type nano TiO 2for raw material, under hydrothermal reaction condition, manufacture the nanoscale precursor powder of Li-Ti-O ternary system at ambient pressure;
Step 2: raw material, auxiliary material, interpolation auxiliary agent are made suspension slurry, then solution is passed through special nozzle under a certain pressure, formation drop nebulizes and sprays into temperature constant in the roasting apparatus of specified scope, carries out drying process, obtains spherical lithium titanate precursor powder.
2. manufacture the technique of lithium titanate lithium ion battery negative material according to claim 1, it is characterized in that, add organic media in described step 2 as bonding agent and carbon source.
3. manufacture the technique of lithium titanate lithium ion battery negative material according to claim 1, it is characterized in that, described withering drying time is less than or equal to 10 minutes.
4. manufacture the technique of lithium titanate lithium ion battery negative material according to claim 1, it is characterized in that, the steady temperature of described roasting apparatus is 1000 degree.
5. manufacture the technique of lithium titanate lithium ion battery negative material according to claim 1, it is characterized in that, described technique also comprises carries out conductive carbon coating modification.
CN201510678156.XA 2015-10-20 2015-10-20 Technology for preparing lithium titanate lithium-ion battery anode material Pending CN105244491A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510678156.XA CN105244491A (en) 2015-10-20 2015-10-20 Technology for preparing lithium titanate lithium-ion battery anode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510678156.XA CN105244491A (en) 2015-10-20 2015-10-20 Technology for preparing lithium titanate lithium-ion battery anode material

Publications (1)

Publication Number Publication Date
CN105244491A true CN105244491A (en) 2016-01-13

Family

ID=55042050

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510678156.XA Pending CN105244491A (en) 2015-10-20 2015-10-20 Technology for preparing lithium titanate lithium-ion battery anode material

Country Status (1)

Country Link
CN (1) CN105244491A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103779540A (en) * 2014-01-15 2014-05-07 合肥国轩高科动力能源股份公司 Lithium-ion cell material synthesis device and synthesis method thereof
WO2014194996A1 (en) * 2013-06-05 2014-12-11 Clariant Produkte (Deutschland) Gmbh Process for the preparation of lithium titanium spinel and its use
CN104409712A (en) * 2014-09-19 2015-03-11 四川省有色冶金研究院有限公司 Preparation method of carbon and nitrogen coated lithium titanate material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014194996A1 (en) * 2013-06-05 2014-12-11 Clariant Produkte (Deutschland) Gmbh Process for the preparation of lithium titanium spinel and its use
CN103779540A (en) * 2014-01-15 2014-05-07 合肥国轩高科动力能源股份公司 Lithium-ion cell material synthesis device and synthesis method thereof
CN104409712A (en) * 2014-09-19 2015-03-11 四川省有色冶金研究院有限公司 Preparation method of carbon and nitrogen coated lithium titanate material

Similar Documents

Publication Publication Date Title
Gangaja et al. Reuse, recycle, and regeneration of LiFePO4 cathode from spent lithium-ion batteries for rechargeable lithium-and sodium-ion batteries
Tian et al. High-rate and cycling-stable nickel-rich cathode materials with enhanced Li+ diffusion pathway
Zu et al. Activated Li2S as a high-performance cathode for rechargeable lithium–sulfur batteries
Liu et al. Self-supported Li4Ti5O12–C nanotube arrays as high-rate and long-life anode materials for flexible Li-ion batteries
Lyu et al. Carbon coated porous titanium niobium oxides as anode materials of lithium-ion batteries for extreme fast charge applications
CN103456936B (en) Sodium ion secondary battery and the preparation method of layered titanate active substance, electrode material, both positive and negative polarity and active substance
Sinha et al. Synthesis and characterization of carbon-coated LiNi1/3Co1/3Mn1/3O2 in a single step by an inverse microemulsion route
Bai et al. Ionic conductor of Li2SiO3 as an effective dual-functional modifier to optimize the electrochemical performance of Li4Ti5O12 for high-performance Li-ion batteries
US20140106223A1 (en) METHODS FOR SURFACE COATING OF CATHODE MATERIAL LiNi0.5-XMn1.5MXO4 FOR LITHIUM-ION BATTERIES
Reddy et al. Mixed Oxides,(Ni1–x Zn x) Fe2O4 (x= 0, 0.25, 0.5, 0.75, 1): Molten Salt Synthesis, Characterization and Its Lithium-Storage Performance for Lithium Ion Batteries
Moorhead-Rosenberg et al. In situ mitigation of first-cycle anode irreversibility in a new spinel/FeSb lithium-ion cell enabled via a microwave-assisted chemical lithiation process
Liang et al. Heuristic design of cathode hybrid coating for power‐limited sulfide‐based all‐solid‐state lithium batteries
Guo et al. Novel strategy of constructing hollow Ga2O3@ N-CQDs as a self-healing anode material for lithium-ion batteries
CN105680013A (en) Preparation method for silicon/graphite/carbon composite negative electrode material of lithium ion battery
CN107293704B (en) Carbon coating lithium sulfide nanocrystal composite, preparation method and application
Du et al. High-energy and long-cycling all-solid-state lithium-ion batteries with Li-and Mn-rich layered oxide cathodes and sulfide electrolytes
WO2023124356A1 (en) Sodium ion battery positive electrode material with multi-core type core-shell structure and preparation method therefor
CN105280912A (en) Preparation method of oxide-cladding lithium ion battery positive material
Zhang et al. A review on electrode materials of fast‐charging lithium‐ion batteries
Zhu et al. Modulating precursor nanosheets for stabilized Ni-rich cathode material for Li-ion batteries
JP6568333B1 (en) Positive electrode active material, method for producing the same, positive electrode, and lithium ion battery
Shu et al. Boosting the electrochemical performance of Li1. 2Ni0. 13Co0. 13Mn0. 54O2 by rough coating with the superionic conductor Li7La3Zr2O12
Wang et al. Nitrogen-doped carbon coated Na3V2 (PO4) 2F3 derived from polyvinylpyrrolidone as a high-performance cathode for sodium-ion batteries
Khalili Azar et al. Enhanced Electrochemical Performance and Thermal Stability of ZrO2-and rGO–ZrO2-Coated Li [Ni0. 8Co0. 1Mn0. 1] O2 Cathode Material for Li-Ion Batteries
Lin et al. Stabilization of high-energy cathode materials of metal-ion batteries: control strategies and synthesis protocols

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160113

RJ01 Rejection of invention patent application after publication